CN108946756A - A kind of multi-stage porous EUO structure molecular screen and its synthetic method - Google Patents
A kind of multi-stage porous EUO structure molecular screen and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of multi-stage porous EUO structure molecular screen and its synthetic methods, it is characterized in that using long chain silane compound as crystallization promoting agent, using the bi-quaternary ammonium salt of double hexa-member heterocycle group alkane substitute structures as organic formwork agent, silicon-aluminum sol is synthesized with crystallization under 2~20 DEG C/h heating rate to target temperature, the target crystallization synthesis temperature is 150~190 DEG C；Then multi-stage porous EUO structure molecular screen original powder is obtained by separating, washing, drying, roast removing organic formwork agent, then successively obtains H-type multi-stage porous EUO structure molecular screen after ammonium ion exchange, drying, roasting.Zeolite molecular sieve provided by the invention has hierarchical porous structure, and product silica alumina ratio range is wide in range, and crystallite dimension is small and relative crystallinity is high, and hydrothermal stability is strong；Reaction evaluating shows good xylene isomerization activity and selectivity, thus has good prospects for commercial application.
Description
Technical field
The present invention relates to the EUO structure molecular screens and its synthetic method of a kind of multi-stage porous, belong to inorganic material synthesis neck
Domain.
Background technique
There is one-dimensional ten-ring 0.54nm × 0.41nm in [100] direction in EUO type topological structure crystal structure of molecular sieve
Duct also has deep 0.81nm twelve-ring 0.68nm × 0.58nm side pocket in the two sides in ten-ring duct.EU-1, ZSM-50 and
TPZ-3 molecular sieve all has EUO type topological structure, and wherein EU-1 molecular sieve is the more extensive molecular sieve of Recent study, by
In its special cellular structure and acidic character, as the difunctional of isomerization of C-8 aromatics acidity of catalyst constituent element preparation
Catalyst shows good activity and selectivity, quilt in the isopropylation catalysis reaction of C8 aronmatic hysomer, benzene
It is described as the first choice of the xylene isomerization catalysis material of a new generation.
US4537754 discloses a kind of hydrothermal crystallizing synthetic method of EU-1 type molecular sieve, with polymethylene α-ω-diamines
The alkyl derivative of ion or its precursor are template, after mixing by silicon and aluminum source, alkali metal, template and crystal seed etc.
It is made through hydrothermal crystallizing.US65144479 discloses a kind of method of hydrothermal synthesis EUO type molecular sieve, by silicon and aluminum source, alkali metal,
Hydro-thermal process, the method simultaneously reduce crystallite dimension, gained crystal grain ruler using ultrasonication after mixing for template and crystal seed etc.
It is very little within 5 μm.(same, hetero-seeds effect in EU-1 Zeolite synthesis, the petroleum journal (PETROLEUM PROCESSING) such as Li Xiaofeng
Supplementary issue in 2006: 93-95) investigate same, hetero-seeds effect in EU-1 Zeolite synthesis.Product can be improved in addition homogeneity crystal seed
Crystallinity, and crystallization time is foreshortened to 1~2 day.Gained EU-1 molecular sieve be it is oval, size be 1.0 μm of 2.0 μ m.Lee
Xiao Feng etc. (rapid synthesis and characterization of EU-1 molecular sieve, petrochemical industry, 2007,36 (8): 794-798) is reported using solid phase
In situ conversion process is in HMBr2-Na2O-Al2O3-SiO2-H2The method of rapid synthesis high-crystallinity EU-1 molecular sieve, water in O system
The thermal synthesis time can foreshorten to 28 hours.The aggregate that EU-1 molecular sieve obtained by the method is 1~5 μm, by 0.3~0.8 μm of Asia
Particle aggregation forms.US6377063 patent discloses a kind of synthetic method of EUO structure molecular screen, using at least one more existing
There is the alkyl derivative of template disclosed in technology or the safer cheap methylene diamine ion of template precursor as knot
Structure directed agents can reduce production cost, safer environmental protection.
EUO structure molecular screen preparation method disclosed in document above mainly has conventional hydrothermal method and solid phase in-situ method, but
Molecular sieve structure is almost the same, and partial size is generally larger, in the micron-scale, and stray crystal is easy to appear, for molecular sieve catalytic
There is serious limitation in service life, and product yield is to be improved.Multistage pore canal EUO structure molecular screen will shorten molecule diffusion away from
From so that reaction product is easier to be diffused into outer surface from active sites, it is suppressed that the formation of coking increases the longevity of catalyst
Life.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the deficiencies in the prior art, and provide a kind of multi-stage porous
EUO structure molecular screen and its synthetic method and application, multi-stage porous EUO structure molecular screen can as catalyst activity component or carrier
To improve catalytic reaction activity, the probability of reaction inactivation is reduced, increases catalyst life；Synthetic method utilizes long chain silane chemical combination
Object replaces the bi-quaternary ammonium salt of alkane substitute to synthesize multistage pore canal as organic formwork agent as crystallization promoting agent, using double hexa-member heterocycle groups
The molecular sieve of the method for EUO structure molecular screen, this pore size distribution structure is conducive to C8The acidic components of aromatics isomerization reaction.
To achieve the goals above, the present invention adopts the following technical scheme:
Present invention firstly provides a kind of synthetic methods of multi-stage porous EUO structure molecular screen, comprising the following steps:
(1) prepare mixed sols: by alkali source, silicon source, silicon source, long chain organic silanes LCS, bi-quaternary ammonium salt template OSDA and
Deionized water H2O is uniformly mixed, and obtains mixed sols；In mixed sols, alkali source is with Na2O meter, silicon source is with SiO2Meter, silicon source with
Al2O3Meter, each molar ratio of material are Na2O:SiO2: Al2O3: LCS:OSDA:H2O=(0.02~0.2): 1.0:(0.001667~
0.05): (0.003~0.03): (0.05~0.5): (10~50)；
(2) crystallization: the mixed sols that step (1) obtains is placed in crystallizing kettle, crystallization under conditions of 150~200 DEG C
24~168 hours, after crystallization is complete, isolate solid product, solid product is washed, removes organic mould after dry, roasting
Plate agent obtains the original powder of multi-stage porous EUO structure molecular screen；
(3) ion exchange: it is de- that the original powder for the multi-stage porous EUO structure molecular screen that step (2) is obtained carries out ammonium ion exchange
Except Na+Ion obtains the porous grade EUO structure molecular screen of H-type after product drying, roasting；
In step (1), the bi-quaternary ammonium salt template OSDA is selected from the knot containing double hexa-member heterocycle group alkane substitutes
The compound of structure, structural formula is as shown in Formula I, Formulae II and formula iii:
The Formula I of n=4~12；
The Formulae II of n=4~12；
The formula iii of n=4~12；
The porous grade EUO structure molecular screen formed in step (3), including EU-1 molecular sieve, TPZ-3 molecular sieve and ZSM-50
Any one in molecular sieve, the molar ratio of silica/alumina is in 20~600 ranges in molecular sieve.
In above-mentioned technical proposal, the synthetic method, specifically includes the following steps:
(1) it prepares mixed sols: the long chain organic silanes LCS of the ratio being dissolved in methanol or ethyl alcohol and is allowed to molten
Solution, and it is dispersed with stirring the solution to form long chain organic silanes LCS；Then described in being added into the solution of long chain organic silanes LCS
Alkali source, silicon source, bi-quaternary ammonium salt template OSDA and the deionized water H of ratio2It is small to stir 5~10 under the conditions of 25~60 DEG C by O
When, obtain silicon source mixed solution；Under conditions of 25~80 DEG C, the silicon source of the ratio is added to the silicon source mixed solution
In, after being vigorously stirred 30~180min, it is stored at room temperature ageing 2~24 hours and obtains mixed sols；
(2) crystallization: the mixed sols that step (1) obtains is placed in crystallizing kettle, in 150~190 DEG C of item of target temperature
Crystallization under part, initial heating rate are 2~20 DEG C/h, are warming up to after target temperature and carry out crystallization at a temperature of holding, are heated up
Expending the time is 6.5~85 hours, and it is 24~168 hours that crystallization, which takes time, after crystallization is complete, is centrifugated out solid production
Object washs solid product with deionized water to neutrality, then 12~48 hours dry under the conditions of 100~130 DEG C, drying repeatedly
2~10 hours removing organic formwork agents are roasted under the conditions of 500~600 DEG C afterwards, obtain the original of multi-stage porous EUO structure molecular screen
Powder；
(3) original powder for the multi-stage porous EUO structure molecular screen that step (2) obtains ion exchange: is placed in NH4 +Solion
In, it is exchanged 2~12 hours at 80~120 DEG C, is then centrifuged for or filters to isolate ion exchange product, ion exchange product is used
Deionized water is washed repeatedly to neutrality；Repeat above-mentioned NH4 +Ion exchange process 1~3 time, then dry 12 at 100~130 DEG C
~48h roasts 2~10 hours at 400~600 DEG C after dry, obtains the multi-stage porous EUO structure molecular screen of H-type.
In above-mentioned technical proposal, in step (1), the alkali source is NaOH, Na2O2、KOH、Na2CO3、NaHCO3In appoint
It anticipates a kind of, two kinds or more the mixtures being mixed in any proportion.
In above-mentioned technical proposal, in step (1), the silicon source be waterglass, silica solution, silester, methyl silicate,
In sodium metasilicate, silicic acid, diatomite, silica gel microball or White Carbon black any one, two kinds or more be mixed in any proportion
Mixture.
In above-mentioned technical proposal, in step (1), the silicon source be boehmite, aluminum nitrate, aluminum sulfate, aluminium chloride,
In aluminium hydroxide, aluminium isopropoxide or Aluminum sol any one, two kinds or more the mixtures being mixed in any proportion.
In above-mentioned technical proposal, in step (1), the long chain organic silanes LCS be hexadecyl trimethoxy silane,
Hexadecyl, octadecyl trimethoxysilane, octadecyltriethoxy silane, octadecyl methyl two
In methoxy silane, octadecyldimethyl methoxy silane any one, two kinds or more be mixed in any proportion
Mixture.
In above-mentioned technical proposal, in step (1), the bi-quaternary ammonium salt template OSDA is specially bis- (the N- methyl of 1,6-
Piperidines) hexane, bis- (N- methyl piperidine) butane of 1,4-, bis- (N- methyl piperidine) pentanes of 1,5-, bis- (the N- methyl piperazines of 1,7-
Pyridine) heptane, bis- (N- methyl piperidine) octanes of 1,8-, bis- (N methyl piperazine) butane of 1,4-, the bis- (N methyl piperazines of 1,5-
) pentane, bis- (N methyl piperazine) hexanes of 1,6-, bis- (N methyl piperazine) octanes of 1,8-, the bis- (N-methylmorpholines of 1,4-
) butane, bis- (N-methylmorpholine) pentanes of 1,5-, bis- (N-methylmorpholine) hexanes of 1,6-, the bis- (N-methylmorpholines of 1,8-
) it is any one or several in octane, bis- (N- methyl piperidine) hexanes of preferably 1,6-, bis- (N methyl piperazine) hexanes of 1,6-,
In bis- (N-methylmorpholine) hexanes of 1,6- any one, two kinds or more the mixtures being mixed in any proportion.
In above-mentioned technical proposal, in step (3), the NH4 +Solion refers to that the aqueous solution of ammonium salt, ammonium salt are
Ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, in ammonium acetate any one, two kinds or more be mixed in any proportion
Mixture；In the aqueous solution of ammonium salt, the concentration of ammonium salt is 0.1~5.0mol/L, preferably 0.2~2.0mol/L.
In above-mentioned technical proposal, in step (3), the original powder and NH of multi-stage porous EUO structure molecular screen4 +The solid-liquid of solion
Mass ratio is 1:(5~50).
The present invention also provides a kind of multi-stage porous EUO structure molecular screens of H-type by the synthesis of above-mentioned synthetic method, including
Any one in EU-1 molecular sieve, TPZ-3 molecular sieve and ZSM-50 molecular sieve, preferably EU-1 molecular sieve；Silica in molecular sieve/
The molar ratio of aluminium oxide is in 20~600 ranges.
The advantages of technical solution of the present invention, is:
1, the EUO molecular sieve relative crystallinity that the present invention synthesizes is high, and crystallite dimension is small, has micropore-mesopore-macropore more
Grade cellular structure, is conducive to reactant molecule and spreads on its catalyst activity position, increases external surface area, improves molecular sieve
Diffusion further increases catalytic activity.
2, present invention synthesis EUO molecular sieve is using the novel double quaternary ammoniums of the structure containing double hexa-member heterocycle group alkane substitutes
Salt overcomes the shortcomings that prior art cannot obtain high silicon EU-1 zeolite as template, and Zeolite synthesis is reproducible, feeds intake
Range is wide in range, and synthesis condition limitation is few, and product silica alumina ratio range is wide, and hydrothermal stability is strong, advantageously accounts for prior art report
EU-1 zeolite synthetic product silica alumina ratio is low, the not high problem of single-autoclave yield rate.
3, long chain organic silanes be joined in present invention synthesis, increases the electrostatic repulsion forces between primary particles, so that
Grain is less likely to occur to reunite.Methoxyl group or ethyoxyl can replace the non-skeleton ol group on micelle surface, thereby reduce particle
Between attraction, so that established state of aggregation nucleus in solution is spread out, to reduce the trend of reunion.Methanol or ethyl alcohol parent
Aqueous aquation also accelerates nucleation process, increases the relative populations of effective crystal seed, so that zeolite crystal ruler
It is very little to become smaller.
4, the present invention not only optimizes synthesis process, while the zeolite molecular sieve prepared has special construction pattern, improves
The structure feature of product, synthesizes the raw material used and technique is simple, is conducive to industrializing implementation.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram of the molecular sieve of comparative example 1 of the present invention preparation.
Fig. 2 is X-ray diffraction (XRD) spectrogram of molecular sieve prepared by the embodiment of the present invention 1.
Fig. 3 is scanning electron microscope (SEM) photo of the molecular sieve of comparative example 1 of the present invention preparation.
Fig. 4 is scanning electron microscope (SEM) photo of molecular sieve prepared by the embodiment of the present invention 1.
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold:
In each comparative example and embodiment, Jie-macropore volume of molecular sieve and the measuring method of total pore volume are as follows: according to
RIPP151-90 standard method (" petrochemical egineering analysis method (RIPP test methods) ", Yang Cui is surely equal to be compiled, Science Press,
Nineteen ninety publishes) total pore volume of molecular sieve is determined according to adsorption isotherm, then surveyed from adsorption isotherm according to T graphing method
Total pore volume is subtracted micro pore volume and obtains Jie-macropore volume by the micro pore volume for making molecular sieve.
In each comparative example and embodiment, the measurement of crystallinity and nSiO2/nAl2O3 select Holland PANalytical type X to penetrate
Line diffractometer, experiment condition are as follows: CuK α radiates (0.1541nm), tube voltage 40kV, tube current 40mA.The measurement of relative crystallinity
It is to be carried out according to SH/T0340-92 standard method (" standard of chemical industry compilation ", China Standards Press publish for 2000)
's.
Comparative example 1:
Synthesize EU-1 molecular sieve according to patent CN01121442 embodiment: by 3530g benzyl dimethyl amine (98%) and
3260g benzyl chlorine (99%) is diluted in 42.92g water, then add 38.45g SiO2 colloidal sol (Ludox HS40,40%
SiO2), the solution I being made of silicon and structural agent precursor is prepared.Then by 0.610g solid sodium hydroxide (99%) and
0.496g solid sodium aluminate (46%A12O3,33%Na2O) is dissolved in 5.36g water, prepares solution II.It under stiring will be molten
Liquid I is added in solution II, and 5.36g water is then added.It is mixed until uniform.The mixture allowed is in 125ml pressure
It is stirred to react 3 days in 180 DEG C at autogenous pressures in kettle.After cooling, filtration product is washed with deionized, then 120 DEG C
Dry 12h, is warming up to 550 DEG C of roasting 4h to get crystallinity to EU-1 molecular sieve, set as 90%, below other samples and this
Sample calculates relative crystallinity as reference.
The original powder of 10g molecular sieve is placed in the NH that 100ml concentration is 0.5mol/L4NO3In solution, 4h is exchanged at 90 DEG C；
Then ion exchange product is filtered to isolate, above-mentioned NH is repeated4 +Ion exchange process 2 times, ion exchange product deionized water
It is washed repeatedly to neutrality, then the dry 12h at 120 DEG C, roasts 4 hours at 550 DEG C after dry, obtains EU-1 points of H-type
Son sieve, is denoted as VS-1.
Comparative example 2:
EU-1 molecular sieve is synthesized according to patent CN201610102491 embodiment: taking 6.0g deionized water and 0.22g hydrogen-oxygen
Change sodium, 0.5g hexamethylene bromide, 1.2g white carbon black (admittedly containing 92%, similarly hereinafter), 0.14g sodium metaaluminate (Al2O3: 41wt%) it is mixed
It closes, stirs 2h, be placed in reaction kettle, carry out first time ageing: 80 DEG C of Aging Temperature, digestion time is for 24 hours.It is added after ageing
γ-glycidyl ether oxygen propyl trimethoxy silicane of silicon source 3mol%.Second of ageing is carried out again: 100 DEG C of Aging Temperature, old
Change time 12h.In 170 DEG C of crystallization 60h, filtering and washing and 120 DEG C of dry 12h after ageing, 550 DEG C of roasting 4h are warming up to,
Obtain EU-1 molecular screen primary powder, relative crystallinity 95%.
The original powder of 10g molecular sieve is placed in the NH4NO3 solution that 100ml concentration is 0.5mol/L, is exchanged at 90 DEG C
4h；Then filter to isolate ion exchange product, repeat above-mentioned NH4+ ion exchange process 2 times, ion exchange product spend from
Sub- water is washed repeatedly to neutrality, and then the dry 12h at 120 DEG C, roasts 4 hours at 550 DEG C after dry, obtain the EU- of H-type
1 molecular sieve, is denoted as VS-2.
Comparative example 3:
EU-1 molecular sieve is synthesized according to patent CN201610255048 embodiment: taking 1.35mol dimethyl stearyl [3-
(trimethoxy silicon substrate) propyl] ammonium chloride, it is dissolved in 16% methanol aqueous solution of 750ml, 300g is added after dissolving completely
The silica of (5mol) specific surface area 200m2/g, partial size 12nm, are poured into 2000ml three-necked flask, 100 DEG C of return stirrings
10h, by obtained solid ethanol washing, 100 DEG C of dryings, grinding obtains the SiO 2 powder of surface silanization.
2.6g sodium hydroxide is added in 10ml distilled water, 2.0g sodium metaaluminate (Al is added after stirring clarification2O3:
41wt%), the double ammonium dissolution clarifications of 17.2g hexamethyl bromination are added after being completely dissolved, add 0.8g sodium fluoride and 0.8g nitric acid
Ammonium is added 0.4g crystal seed and dissolves 20min, is eventually adding the SiO 2 powder of above-mentioned surface silanization after clarification to be dissolved
42.2g stirs 4h at room temperature, obtains silica-alumina gel.
Obtained silica-alumina gel is fitted into the reaction kettle with polytetrafluoroethyllining lining of sealing, 100 DEG C of pre- crystallization 16h,
Then heat to 160 DEG C of crystallization 12 days.Obtained solid product is taken out, is washed to neutrality with distillation, 120 DEG C of dry 12h are warming up to
550 DEG C of logical oxygen roast 4h, obtain mesoporous EU-1 molecular screen primary powder, relative crystallinity 92%.
The original powder of 10g molecular sieve is placed in the NH4NO3 solution that 100ml concentration is 0.5mol/L, is exchanged at 90 DEG C
4h；Then ion exchange product is filtered to isolate, above-mentioned NH is repeated4 +Ion exchange process 2 times, ion exchange product deionization
Water is washed repeatedly to neutrality, and then the dry 12h at 120 DEG C, roasts 4 hours at 550 DEG C after dry, obtain the EU-1 of H-type
Molecular sieve is denoted as VS-3.
Embodiment 1:
A kind of synthetic method of multi-stage porous EUO structure molecular screen, comprising the following steps:
(1) it prepares mixed sols: weighing quantitative hexadecyl trimethoxy silane dissolution and form solution simultaneously in methyl alcohol
It is dispersed with stirring, forms the solution of hexadecyl trimethoxy silane；Then add into the solution of hexadecyl trimethoxy silane
Enter bis- (N- methyl piperidine) hexanes of quantitative NaOH, waterglass, 1,6- and deionized water H2O obtains silicon source mixed solution；?
Under conditions of 60 DEG C, quantitative boehmite is added in silicon source mixed solution, after being vigorously stirred 90min, is stored at room temperature old
Change 12 hours and obtains mixed sols；Mixed sols as crystallization precursor mixture, consisting of:
Na2O:SiO2:Al2O3:LCS:OSDA:H2O=0.12:1:0.0211:0.0042:0.08:15.
(2) crystallization: the mixed sols that step (1) obtains is placed in crystallizing kettle, crystallization under conditions of 170 DEG C, wherein
The heating rate for rising to 170 DEG C from room temperature is 5 DEG C/h, and crystallization time is 72 hours, and after crystallization is complete, room is chilled to after taking-up
Temperature is centrifugated out solid product, washs solid product repeatedly with deionized water to neutrality, then drying under the conditions of 120 DEG C
24 hours, 6 hours removing organic formwork agents were roasted under the conditions of 550 DEG C after dry, obtain the original of multi-stage porous EUO structure molecular screen
Powder.Selected silicon source, silicon source, long chain organic silanes, bi-quaternary ammonium salt Template Type and charge ratio, heating rate, crystallization
Temperature, crystallization time, product silica alumina ratio and materialization characterization are as shown in table 2 and table 3.
(3) original powder for the 10g multi-stage porous EUO structure molecular screen that step (2) obtains ion exchange: is placed in 100ml concentration
For the NH of 0.5mol/L4In Cl solution, 4h is exchanged at 90 DEG C；Then ion exchange product is filtered to isolate, ion exchange produces
Object is washed repeatedly with deionized water to neutrality；Repeat above-mentioned NH4 +Ion exchange process 2 times, then the dry 12h at 120 DEG C, does
It is roasted 4 hours at 550 DEG C after dry, obtains the multi-stage porous EUO structure molecular screen of H-type, be denoted as EUO-1.
The original powder for the multi-stage porous EUO structure molecular screen that the present invention obtains, relative crystallinity 102%.
The EU-1 zeolite product that the present invention obtains has the hierarchical porous structure of micropore-mesopore, mesopore orbit size range 2
~15nm.
XRD characterization is carried out to be confirmed as EU-1 molecular sieve to sample 1 (EUO-1) prepared in embodiment 1 to the present invention:
Used instrument is PANalytical X ' Pert type X-ray diffractometer, and copper target, K α radiation source instrument operating voltage is 40kv,
Operating current is 40mA.Typical XRD spectrum (such as Fig. 2) is representative with sample 1,2 θ 5 °~50 ° main diffraction peak positions and
Peak intensity is as shown in table 1.Other sample data results are compared with sample 1, and diffraction maximum location and shape are identical, according to synthesis condition
Change relative peak intensities fluctuation in ± 5% range, shows that synthetic product has the feature of EU-1 molecular sieve structure, XRD spectra
If Fig. 2 analysis obtain, 2 θ=7.93 °, 8.70 °, 19.10 °, 20.55 °, 22.20 °, 27.20 ° place diffraction maximum be main feature
Peak.
Table 1
SEM map analysis is carried out to sample 1 prepared in embodiment 1 to the present invention, showing from the SEM map analysis of Fig. 4 can
Know, EU-1 molecular sieve is that the nanocrystal of sheet assembles pattern, and BET is analysis shows that specific surface area is 547.8m2/ g, mesoporous Kong Rong
For 0.55cm3/ g, mesoporous average-size are 8.7nm.
Embodiment 2-8:
It is synthesized using synthetic method same as Example 1, it is selected silicon source, silicon source, long chain organic silanes, double
The parameter selections such as quaternary ammonium salt template type and charge ratio, heating rate, crystallization temperature, crystallization time, referring to table 2；Implement
The physical and chemical performance for product E UO-2-EUO-8 that example 2-8 is prepared is as shown in table 3:
Table 2: in embodiment in EU-1 Zeolite synthesis method parameter selection
Table 3: embodiment and comparative example synthesizes EU-1 zeolite product physical and chemical performance
Application Example
Product VS-1~VS-3 the product that will be obtained in EUO-1~EUO-5 product obtained in embodiment 1-5 and comparative example
Carry out catalytic applications evaluation analysis:
Catalysis reaction carries out on fixed bed high-pressure micro-device, using meta-xylene (MX) as reaction raw materials.It measures respectively
Take the particle obtained after 2ml embodiment and comparative example molecular sieve tabletting as catalyst, having a size of 40~60 mesh, and be allowed to etc.
The quartz sand of volume is mixed, and is filled into the flat-temperature zone of reaction tube, and catalyst bed both ends are propped up with quartz sand respectively
Support, the outer end of quartz sand is filled again with suitable silica wool to prevent catalyst loss.100ml/ of the catalyst at 350 DEG C
The H of min2It is reacted after being activated 1 hour under air-flow.
Reaction condition are as follows: 390 DEG C, 0.9MPa, hydrogen to oil volume ratio 800:1, feedstock quality air speed 5.0h-1.The product of reaction
It is analyzed with 7820 type gas-chromatography of Agilent, using fid detector.The results are shown in Table 4 for catalytic evaluation.
Evaluation index: according to activity (meta-xylene conversion ratio CMX/%With paraxylene PX balanced contents value PX/ Σ X/%)
And selectivity (PX/OX ratio, xylene loss XL/ %) evaluation catalyst performance.
It related calculation formula based on constituent mass content and is defined as follows:
Σ X=PX+OX+MX
PX balanced contents value: PX/ Σ X=PX/ (PX+MX+OX) × 100%
OX balanced contents value: OX/ Σ X=OX/ (PX+MX+OX) × 100%
MX balanced contents value: MX/ Σ X=MX/ (PX+MX+OX) × 100%
Table 4: molecular sieve catalyst MX isomerization evaluation result
| Embodiment number | Molecular sieve | CMX/ % | PX/ Σ X/% | OX/ Σ X/% | PX/OX ratio | XL/ % |
| Embodiment 9 | EUO-1 | 45.4 | 23.7 | 19.1 | 1.2 | 2.6 |
| Embodiment 10 | EUO-2 | 46.2 | 23.7 | 18.5 | 1.3 | 4.0 |
| Embodiment 11 | EUO-3 | 46.3 | 23.8 | 19.0 | 1.3 | 3.5 |
| Embodiment 12 | EUO-4 | 47.1 | 23.6 | 19.7 | 1.2 | 3.8 |
| Embodiment 13 | EUO-5 | 46.1 | 23.1 | 18.5 | 1.3 | 4.5 |
| Embodiment 14 | VS-1 | 45.1 | 13.5 | 6.4 | 2.1 | 25.2 |
| Embodiment 15 | VS-2 | 30.7 | 13.4 | 10.0 | 1.3 | 7.4 |
| Embodiment 16 | VS-3 | 44.6 | 14.3 | 14.3 | 1.0 | 16.0 |
As can be seen from Table 4, EUO-1~EUO-5 molecular sieve provided in an embodiment of the present invention is prepared into catalyst, with MX
For starting isomericization reaction in, MX conversion ratio (CMX/ %) >=45.4%, PX balanced contents value (PX/ Σ X/%) >=23.1%, base
Originally reach thermodynamic equilibrium value, xylene loss (XL/ %) < 5%.In contrast, the Hydrogen EUO molecule that comparative example 1 provides
Although sieve VS-1 has higher MX conversion ratio 45.1%, but PX/ Σ X/% value only has 13.5%, XL/ % value reaches 25.2%,
Illustrate that side reaction increases；The MX conversion ratio for the Hydrogen EUO molecular sieve VS-2 that comparative example 2 provides is low, only reaches 30.7%, PX/ Σ
X/% value only has 13.4%, XL/ % value reaches 7.4%.The Hydrogen EUO molecular sieve VS-3 that comparative example 3 provides also has higher MX
Conversion ratio 44.6%, PX/ Σ X/% value only have 14.3%, XL/ % value reaches 16.0%, and side reaction increases.
The above comparative illustration, the multi-stage porous EUO molecular sieve of H-type provided in an embodiment of the present invention have the production of higher PX mesh
Product yield, MX conversion ratio and lower xylene loss (XL/ %), illustrate multi-stage porous EU-1 points of synthesis of the embodiment of the present invention
There is the EU-1 molecular sieve that sub- sieve ratio comparative example provides C8 aromatics isomerization to react more excellent activity and selectivity, and reduce
The loss of xylene products, excellent catalytic performance derive from hierarchical porous structure, increase the expansion of target product paraxylene
It dissipates caused by efficiency.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of synthetic method of multi-stage porous EUO structure molecular screen, comprising the following steps:
(1) prepare mixed sols: by alkali source, silicon source, silicon source, long chain organic silanes LCS, bi-quaternary ammonium salt template OSDA and go from
Sub- water H2O is uniformly mixed, and obtains mixed sols；In mixed sols, alkali source is with Na2O meter, silicon source is with SiO2Meter, silicon source is with Al2O3
Meter, each molar ratio of material are Na2O:SiO2: Al2O3: LCS:OSDA:H2O=(0.02~0.2): 1.0:(0.001667~
0.05): (0.003~0.03): (0.05~0.5): (10~50)；
(2) crystallization: the mixed sols that step (1) obtains is placed in crystallizing kettle, under conditions of 150~200 DEG C crystallization 24~
168 hours, after crystallization is complete, isolate solid product, solid product is washed, removes organic formwork agent after dry, roasting,
Obtain the original powder of multi-stage porous EUO structure molecular screen；
(3) ion exchange: the original powder for the multi-stage porous EUO structure molecular screen that step (2) is obtained carries out ammonium ion exchange removing Na+
Ion obtains the porous grade EUO structure molecular screen of H-type after product drying, roasting；
In step (1), the bi-quaternary ammonium salt template OSDA is selected from the structure containing double hexa-member heterocycle group alkane substitutes
Compound, structural formula is as shown in Formula I, Formulae II and formula iii:
The porous grade EUO structure molecular screen formed in step (3), including EU-1 molecular sieve, TPZ-3 molecular sieve and ZSM-50 molecule
Any one in sieve, the molar ratio of silica/alumina is in 20~600 ranges in molecular sieve.
2. synthetic method according to claim 1, which is characterized in that specifically includes the following steps:
(1) it prepares mixed sols: the long chain organic silanes LCS of the ratio being dissolved in methanol or ethyl alcohol and is allowed to dissolve, and
It is dispersed with stirring the solution to form long chain organic silanes LCS；Then the ratio is added into the solution of long chain organic silanes LCS
Alkali source, silicon source, bi-quaternary ammonium salt template OSDA and deionized water H2O is stirred 5~10 hours under the conditions of 25~60 DEG C, is obtained
Silicon source mixed solution；Under conditions of 25~80 DEG C, the silicon source of the ratio is added in the silicon source mixed solution, acutely
After stirring 30~180min, it is stored at room temperature ageing 2~24 hours and obtains mixed sols；
(2) crystallization: the mixed sols that step (1) obtains is placed in crystallizing kettle, under conditions of 150~190 DEG C of target temperature
Crystallization, initial heating rate are 2~20 DEG C/h, are warming up to after target temperature and carry out at a temperature of holding crystallization, and heating expends
Time is 6.5~85 hours, and it is 24~168 hours that crystallization, which takes time, after crystallization is complete, is centrifugated out solid product, is used
Deionized water washs solid product to neutrality repeatedly, then 12~48 hours dry under the conditions of 100~130 DEG C, it is dry after
2~10 hours removing organic formwork agents are roasted under the conditions of 500~600 DEG C, obtain the original powder of multi-stage porous EUO structure molecular screen；
(3) original powder for the multi-stage porous EUO structure molecular screen that step (2) obtains ion exchange: is placed in NH4 +In solion,
2~12h is exchanged at 80~120 DEG C, is then centrifuged for or filters to isolate ion exchange product, ion exchange product deionized water
It is washed repeatedly to neutrality；Repeat above-mentioned NH4 +Ion exchange process 1~3 time, then dry 12~48h at 100~130 DEG C, does
It is roasted 2~10 hours at 400~600 DEG C after dry, obtains the multi-stage porous EUO structure molecular screen of H-type.
3. synthetic method according to claim 2, which is characterized in that in step (1), the alkali source is NaOH, Na2O2、
KOH、Na2CO3、NaHCO3In any one, two kinds or more the mixtures being mixed in any proportion.
4. synthetic method according to claim 2, which is characterized in that in step (1), the silicon source is waterglass, silicon
In colloidal sol, silester, methyl silicate, sodium metasilicate, silicic acid, diatomite, silica gel microball or White Carbon black any one, two kinds and
The mixture being mixed in any proportion above.
5. synthetic method according to claim 2, which is characterized in that in step (1), the silicon source is to intend thin water aluminium
In stone, aluminum nitrate, aluminum sulfate, aluminium chloride, aluminium hydroxide, aluminium isopropoxide or Aluminum sol any one, two kinds or more to appoint
The mixture that meaning ratio mixes.
6. synthetic method according to claim 2, which is characterized in that in step (1), the long chain organic silanes LCS
For hexadecyl trimethoxy silane, hexadecyl, octadecyl trimethoxysilane, three second of octadecyl
Oxysilane, octadecyl methyl dimethoxysilane, in octadecyldimethyl methoxy silane any one, two kinds and
The mixture being mixed in any proportion above.
7. synthetic method according to claim 2, which is characterized in that in step (1), the bi-quaternary ammonium salt template
OSDA is specially bis- (N- methyl piperidine) hexanes of 1,6-, bis- (N- methyl piperidine) butane of 1,4-, bis- (the N- methyl piperidines of 1,5-
) pentane, bis- (N- methyl piperidine) heptane of 1,7-, bis- (N- methyl piperidine) octanes of 1,8-, the bis- (N methyl piperazines of 1,4-
) butane, bis- (N methyl piperazine) pentanes of 1,5-, bis- (N methyl piperazine) hexanes of 1,6-, the bis- (N methyl piperazines of 1,8-
) octane, bis- (N-methylmorpholine) butane of 1,4-, bis- (N-methylmorpholine) pentanes of 1,5-, the bis- (N-methylmorpholines of 1,6-
) hexane, any one or several in bis- (N-methylmorpholine) octanes of 1,8-, bis- (N- methyl piperidine) hexanes of preferably 1,6-,
In bis- (N methyl piperazine) hexanes of 1,6-, bis- (N-methylmorpholine) hexanes of 1,6- any one, two kinds or more to appoint
The mixture that meaning ratio mixes.
8. synthetic method according to claim 2, which is characterized in that in step (3), the NH4 +Solion refers to
The aqueous solution of ammonium salt, ammonium salt be ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, in ammonium acetate any one, two kinds and with
On the mixture that is mixed in any proportion；In the aqueous solution of ammonium salt, the concentration of ammonium salt is 0.1~5.0mol/L.
9. synthetic method according to claim 8, which is characterized in that in step (3), multi-stage porous EUO structure molecular screen
Original powder and NH4 +The solid-liquid mass ratio of solion is 1:(5~50).
10. a kind of multi-stage porous EUO structure molecular screen of the H-type by the described in any item synthetic method synthesis of claim 1-9,
It is characterised in that it includes any one in EU-1 molecular sieve, TPZ-3 molecular sieve and ZSM-50 molecular sieve, silica in molecular sieve/
The molar ratio of aluminium oxide is in 20~600 ranges.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112707407A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Nano linear EUO structure molecular sieve and its synthesis method |
| CN114804145A (en) * | 2021-11-22 | 2022-07-29 | 复榆(张家港)新材料科技有限公司 | Method for directly synthesizing hydrogen type zeolite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105263861A (en) * | 2013-04-02 | 2016-01-20 | 埃克森美孚研究工程公司 | Emm-25 molecular sieve material, its synthesis and use |
| CN105776242A (en) * | 2014-12-19 | 2016-07-20 | 中国石油天然气股份有限公司 | Synthesis method of ZSM-50 molecular sieve |
| CN106830007A (en) * | 2017-03-17 | 2017-06-13 | 中触媒新材料股份有限公司 | With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application |
| CN107151023A (en) * | 2017-06-01 | 2017-09-12 | 嘉兴学院 | The method of the solvent-free solid-phase synthesis synthesis zeolites of ZSM 48 |
-
2018
- 2018-08-20 CN CN201810945479.4A patent/CN108946756B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105263861A (en) * | 2013-04-02 | 2016-01-20 | 埃克森美孚研究工程公司 | Emm-25 molecular sieve material, its synthesis and use |
| CN105776242A (en) * | 2014-12-19 | 2016-07-20 | 中国石油天然气股份有限公司 | Synthesis method of ZSM-50 molecular sieve |
| CN106830007A (en) * | 2017-03-17 | 2017-06-13 | 中触媒新材料股份有限公司 | With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application |
| CN107151023A (en) * | 2017-06-01 | 2017-09-12 | 嘉兴学院 | The method of the solvent-free solid-phase synthesis synthesis zeolites of ZSM 48 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707407A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Nano linear EUO structure molecular sieve and its synthesis method |
| CN114804145A (en) * | 2021-11-22 | 2022-07-29 | 复榆(张家港)新材料科技有限公司 | Method for directly synthesizing hydrogen type zeolite |
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